Tetrazolinone derivatives

ABSTRACT

According to the instant invention there have been found novel tetrazolinone derivatives represented by the general formula (I)                    
     wherein 
     R 1  represents methyl or ethyl, 
     R 2  represents halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl, alkylsulfonyl, phenyl, phenoxy, alkoxycarbonyl, nitro or cyano, and 
     n represents 0, 1, 2, 3, 4 or 5, 
     processes and intermediates for their preparation and their use as herbicides.

This is a 371 of PCT/IB00/00588 filed May 8, 2000.

The present invention relates to novel tetrazolinone derivatives, toprocesses for their preparation and to their use as herbicides.

In Japanese Laid-Open Patent Publications No. 82258/1995, No. 97372/1995and No. 118246/1995 there are disclosed preparation processes of sometetrazolinone derivatives and a preparation process of1-substituted-5(4H)-tetrazolinones, the intermediates thereof. Moreover,the EP-A-146,279 discloses that some tetrazolinone derivatives haveherbicidal activities.

However, the known tetrazolinone derivatives are not fully satisfactorywith regard to their herbicidal activity and their phytotoxicity againstcrops.

According to the invention there have now been found novel tetrazolinonederivatives of the general formula (I)

wherein

R¹ represents methyl or ethyl,

R² represents halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio,haloalkylthio, alkylsulfinyl, alkylsulfonyl, phenyl, phenoxy,alkoxycarbonyl, nitro or cyano, and n represents 0, 1, 2, 3, 4 or 5.

The compounds of the formula (I), according to the invention, can beobtained by a process in which

a) compounds of the general formula (II)

 wherein

R¹ is defined as mentioned above, are reacted with compounds of thegeneral formula (III)

 wherein

R² and n are defined as mentioned above, and

M represents a leaving group such as chloro or bromo

in the presence of an inert solvent and, if appropriate, in the presenceof a base.

The compounds of the formula (I) of the present invention posses strongherbicidal activities and especially demonstrate an excellent herbicidaleffect compared with the known compounds described in the aforementionedEP-A-146,279 which are similar to the compounds of the formula (I). Thecompounds of the invention nevertheless also show a good compatibilitywith crops. Therefore, the compounds of the present invention can bepotentially employed as agrochemicals, specifically as herbicides.

In the formulae mentioned above:

Halogen in “halogen”, “haloalkyl”, “haloalkoxy” and “haloalkylthio”represents fluoro, chloro, bromo or iodo, and preferably fluoro, chloroor bromo.

“Alkyl” may be straight chain or branched chain and there may bementioned, for example, methyl, ethyl, n- or iso-propyl, n-, iso-, sec-or tert-butyl, n- or iso-pentyl, tert-amyl, pentan-3-yl, neopentyl andn-hexyl.

“Alkoxy” may be straight chain or branched chain and there may bementioned, for example, methoxy, ethoxy, propoxy, isopropoxy, n-, iso-,sec- or tert-butoxy, n-pentyloxy and n-hexyloxy.

“Alkylthio” may be straight chain or branched chain and there may bementioned, for example, methylthio, ethylthio, n-propylthio,isopropylthio and n-butylthio.

“Alkylsulfinyl” may be straight chain or branched chain and there may bementioned, for example, methylsulfinyl, ethylsulfinyl, n-propylsulfinyl,isopropylsulfinyl and n-butylsulfinyl.

“Alkylsulfonyl” may be straight chain or branched chain and there may bementioned, for example, methylsulfonyl, ethylsulfonyl, n-propylsulfonyl,isopropyl-sulfonyl and n-butylsulfonyl.

“Haloalkyl” may be straight chain or branched chain and there may bementioned, for example, difluoromethyl, trifluoromethyl, 2-fluoroethyl,2-chloroethyl, 2-bromoethyl, 2,2,2-trifluoroethyl,1,1,2,2-tetrafluoroethyl, 1,1,2,2,2-pentafluoroethyl,2,2,3,3,3-pentafluoropropyl, 3-chloropropyl, 1,3-difluoropropan-2-yl,1,1,1-trifluoropropan-2-yl, 2,2,3,3,4,4,4-heptafluorobutyl and3-bromopropyl.

The Haloalkyl part of “haloalkoxy” and “haloalkylthio” may be as definedin the above-mentioned “haloalkyl”.

As “alkoxycarbonyl” there may be mentioned, for example,methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyland n-butoxycarbonyl.

As a preferable group of compounds of the present invention there can bementioned the compounds of the aforementioned formula (I) wherein

R¹ represents methyl or ethyl,

R² represents fluoro, chloro, bromo, C₁₋₄ alkyl, C₁₋₄ haloalkyl, C₁₋₄alkoxy, C₁₋₄ haloalkoxy, C₁₋₄ alkylthio, C₁₋₄ haloalkylthio, C₁₋₄alkylsulfinyl, C₁₋₄ alkylsulfonyl, phenyl, phenoxy, C₁₋₄ alkoxycarbonyl,nitro or cyano, and n represents 0, 1, 2, 3 or 4.

As a more preferable group of compounds of the present invention therecan be mentioned the compounds of the aforementioned formula (I) wherein

R¹ represents methyl,

R² represents fluoro, chloro, methyl, ethyl, n-propyl, isopropyl,tert-butyl, trifluoromethyl, methoxy, ethoxy, isopropoxy,trifluoromethoxy, difluoromethoxy, 2,2,2-trifluoroethoxy, methylthio,ethylthio, isopropylthio, methysulfinyl, methylsulfonyl, phenyl,phenoxy, methoxycarbonyl, ethoxycarbonyl, nitro or cyano, and nrepresents 0, 1, 2, or 3.

Among the compounds of the aforementioned formula (I) there may beespecially pointed out the compounds which are represented by thefollowing formula

wherein the carbon atom marked with * represents an asymmetric carbonatom and R¹ and R² have the same meaning as mentioned above. Based onthis fact the compounds of the present invention can exist as pureoptically active enantiomers or in a form of optional mixtures ofoptically active enantiomers. Therefore, the compounds of theaforementioned formula (I) of the present invention include opticallyactive substances and mixtures thereof.

Using, for example, 1-((S)-α-methylbenzyl)-5(4H)-tetrazolinone andN-isopropyl-N-phenylcarbamoyl chloride as the starting materialsaccording to preparation process a), the said preparation process can beillustrated by the following reaction scheme:

The compounds of the formula (II), which are used as the startingmaterials in the aforementioned preparation process a) are novelcompounds, which were not described in literature, and can be prepared,for example, by the following proccesses in which

according to process variant b) compounds of the general formula (IV)

 wherein

R¹ is defined as mentioned above,

are reacted with trimethylsilyl azide in the presence of a catalyticamount of boron trifluoride-ether-complex, or

according to process variant c) compounds of the above-mentioned generalformula (IV) are reacted with sodium azide in a polar solvent in thepresence of a catalytic quantity of aluminium chloride.

The compounds of the general formula (IV) which are used as the startingmaterial in the above-mentioned preparation process variants b) and c)include isocyanates known in the area of organic chemistry and can beeasily obtained, for example, by reacting amines of the general formula(V)

wherein

R¹ is as defined above,

with, for example, phosgene according to known methods described, forexample, in “SHIN JIKKEN KAGAKU KOUZA” (New experimental chemistrylecture) Vol. 14, III, pp.1490-1496 (published by Maruzen Ltd. on Feb.20, 1978).

The compounds of the above-mentioned formula (V) can be synthesized, forexample, similarly to the methods described in “SHIN JIKKEN KAGAKUKOUZA” (New experimental chemistry lecture) Vol. 14, III, pp.1332-1398(published by Maruzen Ltd. on Feb. 20, 1978) or Organic Reactions, Vol.5, 1949, 301-330 (John Wiley & Sons, Inc.).

As compounds of the above-mentioned formula (II) there can be mentionedthe following species:

1-((S)-α-methylbenzyl)-5(4H)-tetrazolinone,

1-((R)-α-methylbenzyl)-5(4H)-tetrazolinone,

1-((S)-α-ethylbenzyl)-5(4H)-tetrazolinone,

1-((R)-α-ethylbenzyl)-5(4H)-tetrazolinone.

The compounds of the formula (III) to be reacted with the compounds ofthe above-mentioned formula (II) includeN-isopropyl-N-(substituted)phenylcarbamoyl halides which are well knownin the area of organic chemistry. As typical examples of them there canbe mentioned the following compounds:

N-isopropyl-N-phenylcarbamoyl chloride,

N-isopropyl-N-(4-fluorophenyl)carbamoyl chloride,

N-isopropyl-N-(3-methylphenyl)carbamoyl chloride,

N-isopropyl-N-(4-trifluoromethylphenyl)carbamoyl chloride,

N-isopropyl-N-(2-ethoxyphenyl)carbamoyl chloride,

N-isopropyl-N-(4-difluoromethoxyphenyl)carbamoyl chloride,

N-isopropyl-N-(4-isopropylthiophenyl)carbamoyl chloride,

N-isopropyl-N-(4-methylsulfinylphenyl)carbamoyl chloride,

N-isopropyl-N-(4-methylsulfonylphenyl)carbamoyl chloride,

N-isopropyl-N-(4-2,2,2-trifluoroethylthiophenyl)carbamoyl chloride,

N-isopropyl-N-(4-phenylphenyl)carbamoyl chloride,

N-isopropyl-N-(3-phenoxyphenyl)carbamoyl chloride,

N-isopropyl-N-(2-ethoxycarbonylphenyl)carbamoyl chloride,

N-isopropyl-N-(4-nitrophenyl)carbamoyl chloride,

N-isopropyl-N-(4-cyanophenyl)carbamoyl chloride and the bromidescorresponding to these chlorides.

The reaction of the preparation process a) is usually conducted in aninert organic solvent. As examples of such inert organic solvents therecan be mentioned aliphatic, alicyclic and aromatic hydrocarbons (whichmay optionally be chlorinated), for example, pentane, hexane,cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene,dichloromethane, chloroform, carbon tetetrachloride, 1,2-dichloroethane,chlorobenzene, dichlorobenzene; ethers, for example, diethyl ether,methyl ethyl ether, diisopropyl ether, dibutyl ether, dioxane,dimethoxyethane (DME), tetra-hydrofuran (THF), diethylene glycoldimethyl ether (DGM); nitriles, for example, acetonitrile,propionitrile; acid amides, for example, dimethylformamide (DMF),dimethylacetamide (DMA), N-methylpyrrolidone,1,3-dimethyl-2-imidazolidinone, hexamethylphosphoric triamide (HMPA).

The preparation process a) may be conducted in the presence of a base,preferable in the presence of the base 4-dimethylaminopyridine (DMAP).

In case of using DMAP as a base, the reaction of the preparation processa) is usually conducted at about −10 to about 200° C., preferably about25 to about 140° C. under normal pressure. Optionally it is possible toconduct the reaction under elevated pressure or under reduced pressure.

Moreover, it is possible to conduct the reaction of the preparationprocess a) using other bases than DMAP. As such bases there can bementioned inorganic salts (for example, sodium carbonate, potassiumcarbonate etc.), alkyl alcoholates (for example, sodium methoxide,sodium ethoxide, potassium tert-butoxide), sodium hydroxide, potassiumhydroxide, lithium hydroxide, organic bases (for example, triethylamine,1,1,4,4-tetramethylethylenediamine, N,N-dimethylaniline, pyridine etc.).

In case of conducting said reaction using these bases, the compounds ofthe formula (I) can be selectively obtained by using DMAP as a catalyst.

The reaction temperature in this case may be in the range of usuallyabout 0 to about 150° C., preferably about 25 to about 100° C. Saidreaction is conducted desirably under normal pressure. Optionally,however, it is possible to conduct it under elevated pressure or underreduced pressure.

The desired compounds of the formula (I), according to the presentinvention, can be obtained, for example, by reacting 1 mole of acompound of the formula (II) with about 1 mole to about 1.5 moles of acompound of the formula (III) in the presence of about 1 mole to about1.5 moles of DMAP as a base and in such an inert solvent as mentionedabove. The compounds of the formula (I) can also be prepared by reacting1 mole of a compound of the formula (II) with about 1 mole to about 1.5moles of a compound of the formula (III) in the presence of about 0.01mole to about 0.3 moles of DMAP as a catalyst and, for example, about 1mole to about 1.5 moles of potassium carbonate as a base and in an inertsolvent of the kind as mentioned above.

The compounds of the formula (I), according to the present inventionthus obtained can be isolated and purified, for example, by means ofcrystallization, chromatography etc.

The reaction of the aforementioned preparation process b) can beconducted using a boron trifluoride-ether-complex as a catalyst. Thereaction temperature is usually kept at about 0 to about 200° C.,preferably about 50 to about 150° C. The reaction may be conducteddesirably under normal pressure. Optionally, however, it is possible toconduct it under elevated pressure or under reduced pressure.

The preparation process b) is usually conducted by reacting 1 mole of acompound of the formula (IV) with about 1 mole to about 2 moles oftrimethylsilyl azide in the presence of about 0.005 moles to about 0.01mole of boron trifluoride-ether-complex as a catalyst.

The reaction of the preparation process c) is usually conducted in apolar solvent. As such polar solvent there can be mentioned, forexample, acid amides such as dimethylformamide, dimethylacetamide andsufoxides such as dimethylsulfoxide, sulfolane. The reaction temperaturemay be generally about 0 to about 200° C., preferably about 20 to about150° C. The reaction may be conducted desirably under normal pressure.Optionally, however, it is possible to conduct it under elevatedpressure or under reduced pressure.

The preparation process c) can be conducted by reacting 1 mole of acompound of the formula (IV) with about 1 mole to about 1.5 moles ofsodium azide in the presence of about 0.05 moles to about 1 mole ofaluminum chloride as a catalyst and in a polar solvent, for example,dimethylformamide.

The compounds of the formula (I), according to the present invention,have, as shown in the test examples to be described later, excellentherbicidal activities and can be used as herbicidal agents forcontrolling weeds. “Weeds” in this regard mean, in the broadest sense,all plants which grow in locations where they are undesired.

The compounds, according to the present invention act as total orselective herbicides depending upon the applied concentration. Theactive compounds of the present invention can be used, for example, asselective herbicides between the following weeds and cultures.

Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria,Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Ipomoea,Polygonum, Ambrosia, Cirsium, Sonchus, Solanum, Rorippa, Lamium,Veronica, Datura, Viola, Galeopsis, Papaver, Centaurea, Galinsoga,Rotala, Lindemia etc.

Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus,Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana,Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita etc.

Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum,Digitaria, Phleum, Poa, Festuca, Eleusine, Lolium, Bromus, Avena,Cyperus, Sorghum, Agropyron, Monochoria, Fimbristylis, Sagittaria,Eleocharis, Scirpus, Paspalum, Ischaemum, Agrostis, Alopecurus, Cynodonetc.

Monocotyledon cultures of the genera: Oryza, Zea, Triticum, Hordeum,Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Alliumetc.

According to the invention all plants and plant parts can be treated.The term plants includes all plants and plant populations, such asdesired or undesired wild plants and cultivated plants (includingnaturally occurring cultivated varieties). Cultivated plants can beplant varieties that were obtained by conventional bredding andoptimizing processes or by biotechnological and genetic engineeringmethods or a combination of such processes and methods, includingtransgenic plants and including plant varieties that cannot or can beprotected by plant patents or plant variety rights. Plant parts are allparts and organs of plants occurring above or below the surface of thesoil, e.g. shoots, leaves, needles, stalks and stems, trunks, flowers,fruits and seeds as well as roots, tubers, bulbs and rhizomes. The termplant parts also includes harvested crops and propagation material, e.g.cuttings, tubers, bulbs, rhizomes, shoots and seeds.

According to the invention the plants and plants parts are treated usingthe usual methods by applying the active ingredients or compositionscontaining them directly to the plants or plant parts or to theirsurroundings (including the soil) or storeroom, e.g. by dipping,spraying, dusting, fogging, spreading and in the case of propagationmaterial also by coating using one or multiple layers.

The use of the compounds of the formula (I), according to the present,invention is not restricted to the above-mentioned plants, but may beapplied to other plants in the same manner. The active compounds can,depending upon the applied concentration, non-selectively control weedsand may be used, for example, on industrial terrain, rail tracks, paths,places with or without planted trees.

Moreover, the compounds, according to the present invention, can be usedfor controlling weeds in perennial cultures and applied in, for example,afforestations, decorative tree plantings, orchards, vineyards, citrusgroves, nut orchards, banana plantations, coffee plantations, teaplantations, rubber plantations, oil palm plantations, cocoaplantations, soft fruit plantings, hopfields etc. and can be applied forthe selective controlling of weeds in annual cultures.

The compounds of the formula (I), according to the present invention,can be made into customary agrochemical formulations for theirapplication. As such formulations there can be mentioned,-for example,solutions, emulsions, wettable powders, suspensions, powders, solublepowders, granules, tablets, suspension-emulsion concentrates,microcapsules in polymeric substances, jumbo formulations etc.

The formulations can be prepared according to known methods, forexample, by mixing the compounds of the formula (I) of the presentinvention with extenders, namely liquid diluents and/or solid diluentsor carriers, optionally with surface-active agents, namely emulsifiersand/or dispersants and/or foam-forming agents. When water is used as anextender, for example, organic solvents can be used as auxiliarysolvents.

As liquid diluents or carriers there can be mentioned aromatichydrocarbons (for example, xylene, toluene, alkylnaphthalene etc.),chlorinated aromatic or chlorinated aliphatic hydrocarbons (for example,chlorobenzenes, ethylene chlorides, methylene chloride etc.), aliphatichydrocarbons [for example, cyclohexane etc. or paraffins (for example,mineral oil fractions etc.)], alcohols (for example, butanol, glycolsand their ethers and esters etc.), ketones (for example, acetone, methylethyl ketone, methyl isobutyl ketone, cyclohexanone etc.), stronglypolar solvents (for example, dimethylformamide, dimethylsulphoxide etc.)and water.

As solid diluents there can be mentioned, for example, ground naturalminerals (for example, kaolin, clay, talc, chalk, quartz, attapulgite,montmorillonite, diatomaceous earth etc.), ground synthetic minerals(for example, highly dispersed silicic acid, alumina, silicates etc.)etc.

As solid carriers for granules there can be mentioned, for example,crushed and fractionated rocks (for example, calcite, marble, pumice,sepiolite, dolomite etc.), synthetic granules of inorganic and organicmeals, particles of organic materials (for example, sawdust, coconutshells, maize cobs and tobacco stalks etc.) etc.

As emulsifiers and/or foam-forming agents there can be mentionednonionic and anionic emulsifiers [for example, polyoxyethylene fattyacid esters, polyoxyethylene fatty acid alcohol ethers (for example,alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates,arylsulphonates etc.)], albumin hydrolysis products etc.

As dispersants there are included, for example, ligninsulphite wasteliquor and methyl cellulose.

Tackifiers may also be used in the formulations (powders, granules,emulsions). As usable tackifiers there can be mentioned, for example,carboxymethyl cellulose, natural and synthetic polymers (for example,gum arabic, polyvinyl alcohol, polyvinyl acetate etc.).

Colorants may also be used. As said colorants there can be mentioned,for example, inorganic pigments (for example, iron oxide, titaniumoxide, Prussian Blue etc.), organic dyestuffs such as alizarindyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs, and furthertrace nutrients such as salts of metals such as iron, manganese, boron,copper, cobalt, molybdenum, zinc etc.

Said formulations can contain in a range of generally 0.1-95% by weight,preferably 0.5-90% by weight of the compounds of the aforementionedformula (I).

The compounds of the formula (I) of the present invention can be used assuch or in their formulated forms for controlling weeds. They can beused also as a mixed composition with known herbicides. Such a mixedcomposition can be previously prepared as a final formulation form orcan be prepared by tank-mixing on the occasion of the application.

The compounds of the formula (I) of the present invention can be usedalso with a safener and their application as a selective herbicide maybe broadened by such a mixing. As an example of such safener1-(α,α-dimethylbenzyl)-3-p-tolylurea can be mentioned.

As herbicides, which can be combined with the compounds of the formula(I) of the present invention there can be mentioned, for example, thefollowing known herbicides:

4-amino-6-(1,1-dimethylethyl)-3-ethylthio-1,2,4-triazin-5(4H)-one,1-amino-6-ethylthio-3-(2,2-dimethylpropyl)-1,3,5-triazin-2,4(1H,3H)-dione,or N-(2-benzothiazolyl)-N,N′-dimethylurea etc. (eg. for controllingweeds in cereal cultures);

4-amino-3-methyl-6-phenyl-1,2,4-triazin-5(4H)-one etc. (e.g. forcontrolling weeds in sugar cane cultures);

4-amino-6-(1,1-dimethylethyl)-3-methylthio-1,2,4-triazin-5(4H)-one etc.(e.g. for controlling weeds in soybean cultures);

methyl α-(4,6-dimethoxypyrimidin-2-ylcarbamoylsulfamoyl)-o-toluate etc.(e.g. for controlling weeds in paddy rice culture).

Surprisingly, some of these herbicidal combinations of these herbicideswith compounds of the formula (I) of the present invention showsynergistic effects.

Compounds of the formula (I) of the present invention can be applieddirectly as such or in formulated forms such as ready-to-use solutions,emulsions, suspensions, powders, granules or used in the use formsprepared by further dilution.

The compounds of the formula (I) of the present invention can be appliedby means of, for example, watering, spraying, atomizing, dusting orgranule application etc.

The compounds of the formula (I) of the present invention can be used atany stages before and after germination of plants. They may also bemixed into the soil before sowing.

The application rate of the compounds of the formula (I) of the presentinvention may be varied in a substantial range and is fundamentallydifferent according to the nature of the desired effect. In case ofherbicidal use, as a suitable application rate there can be mentioned,for example, a range of about 0.01 to about 5 kg, preferably about 0.1to about 3 kg of the compounds of the formula (I) of the presentinvention per hectare.

The preparations and applications of the compounds of the presentinvention are described more specifically in the following examples.However, the present invention should not be restricted to them in anyway.

“Parts” mean “parts by weight” unless specified.

SYNTHESIS EXAMPLE 1

1-((S)-α-methylbenzyl)-5(4H)-tetrazolinon (1.00 g),N,N-dimethylaminopyridine (0.77 g) and N-isopropyl-N-phenylcarbamoylchloride (1.25 g) were dissolved in toluene (20 ml) and stirred at 80°C. for 8 hours on heating. After naturally cooling the reaction mixturewas washed with water (2 times with 10 ml), dried with anhydrous sodiumsulfate and then the solvent was distilled off under reduced pressure.The residue was treated by silica gel column chromatography (eluant:hexane: ethyl acetate=3:1) to obtain1-((S)-α-methylbenzyl)-4-(N-isopropyl-N-phenylcarbamoyl)-5(4H)-tetrazolinone(1.72 g). mp: 79-81° C.

The compounds obtained in the same manner as the above-mentionedSynthesis Example are shown in the following Table 1 together with thecompound obtained in the above-mentioned Synthesis Example 1.

TABLE 1

Compound No. R¹ (R²)n *R/S Property 1 CH₃ H racemate 2 CH₃ H R mp 79-81°C. 3 CH₃ H S mp 79-81° C. 4 CH₃ 2-F racemate 5 CH₃ 2-F R n^(D) ₂₀ 1.54216 CH₃ 2-F S n^(D) ₂₀ 1.5386 7 CH₃ 3-F racemate 8 CH₃ 3-F R mp 84-86° C.9 CH₃ 3-F S mp 83-85° C. 10 CH₃ 4-F racemate 11 CH₃ 4-F R mp 68-71° C.12 CH₃ 4-F S mp 67-69° C. 13 CH₃ 2-Cl racemate 14 CH₃ 2-Cl R mp 79-81°C. 15 CH₃ 2-Cl S mp 78-81° C. 16 CH₃ 3-Cl racemate 17 CH₃ 3-Cl R mp75-77° C. 18 CH₃ 3-Cl S mp 76-78° C. 19 CH₃ 4-Cl racemate 20 CH₃ 4-Cl Rmp 68-70° C. 21 CH₃ 4-Cl S mp 68-70° C. 22 CH₃ 2-Br racemate 23 CH₃ 2-BrR 24 CH₃ 2-Br S 25 CH₃ 3-Br racemate 26 CH₃ 3-Br R 27 CH₃ 3-Br S 28 CH₃4-Br racemate 29 CH₃ 2-I racemate 30 CH₃ 3-I racemate 31 CH₃ 4-Iracemate 32 CH₃ 4-Br R 33 CH₃ 4-Br S 34 CH₃ 2-CH₃ racemate 35 CH₃ 2-CH₃R mp 97-100° C. 36 CH₃ 2-CH₃ S mp 94-95° C. 37 CH₃ 3-CH₃ racemate 38 CH₃3-CH₃ R mp 48-52° C. 39 CH₃ 3-CH₃ S mp 55-58° C. 40 CH₃ 4-CH₃ racemate41 CH₃ 4-CH₃ R mp 45-50° C. 42 CH₃ 4-CH₃ S mp 44-47° C. 43 CH₃ 3-C₂H₅racemate 44 CH₃ 4-C₂H₅ racemate 45 CH₃ 4-C₃H₇-n racemate 46 CH₃2-C₃H₇-iso racemate 47 CH₃ 4-C₃H₇-iso racemate 48 CH₃ 4-C₄H₉-tertracemate 49 CH₃ 2-CF₃ racemate 50 CH₃ 2-CF₃ R mp 79-81° C. 51 CH₃ 2-CF₃S mp 78-81° C. 52 CH₃ 3-CF₃ racemate 53 CH₃ 3-CF₃ R n^(D) ₂₀ 1.5209 54CH₃ 3-CF₃ S n^(D) ₂₀ 1.5194 55 CH₃ 4-CF₃ racemate 56 CH₃ 4-CF₃ R mp118-121° C. 57 CH₃ 4-CF₃ S mp 116-118° C. 58 CH₃ 4-OCH₃ racemate 59 CH₃4-OCH₃ R 60 CH₃ 4-OCH₃ S 61 CH₃ 2-OC₂H₅ racemate 62 CH₃ 3-OC₂H₅ racemate63 CH₃ 4-OC₂H₅ racemate 64 CH₃ 4-OC₃H₇-iso racemate 65 CH₃ 3-OCF₃racemate 66 CH₃ 4-OCF₃ racemate 67 CH₃ 4-OCHF₂ racemate 68 CH₃ 4-OCH₂CF₃racemate 69 CH₃ 2-SCH₃ racemate 70 CH₃ 3-SCH₃ racemate 71 CH₃ 4-SCH₃racemate 72 CH₃ 4-SC₂H₅ racemate 73 CH₃ 4-SC₃H₇-iso racemate 74 CH₃4-S(O)CH₃ racemate 75 CH₃ 4-SO₂CH₃ racemate 76 CH₃ 4-SCF₃ racemate 77CH₃ 4-SCH₂CF₃ racemate 78 CH₃

racemate 79 CH₃

racemate 80 CH₃

racemate 81 CH₃ 2-CO₂CH₃ racemate 82 CH₃ 2-CO₂C₂H₅ racemate 83 CH₃ 4-NO₂racemate 84 CH₃ 4-CN racemate 85 CH₃ 2,3-F₂ racemate 86 CH₃ 2,4-F₂racemate 87 CH₃ 2,4-F₂ R n^(D) ₂₀ 1.5319 88 CH₃ 2,4-F₂ S n^(D) ₂₀ 1.532989 CH₃ 2,5-F₂ racemate 90 CH₃ 2,6-F₂ racemate 91 CH₃ 2,6-F₂ R mp 56-60°C. 92 CH₃ 2,6-F₂ S mp 53-58° C. 93 CH₃ 3,4-F₂ racemate 94 CH₃ 3,4-F₂ R95 CH₃ 3,4-F₂ S 96 CH₃ 3,5-F₂ racemate 97 CH₃ 2-F, 4-Cl racemate 98 CH₃2-F, 4-Br racemate 99 CH₃ 2-F, 5-CF₃ racemate 100 CH₃ 2-F, 4-OCH₃racemate 101 CH₃ 3-F, 6-CF₃ racemate 102 CH₃ 3-F, 3-CF₃ racemate 103 CH₃3-F, 4-CH₃ racemate 104 CH₃ 3-F, 5-CH₃ racemate 105 CH₃ 2,3-Cl₂ racemate106 CH₃ 2,4-Cl₂ racemate 107 CH₃ 2,4-Cl₂ R 108 CH₃ 2,4-Cl₂ S 109 CH₃2,6-Cl₂ racemate 110 CH₃ 2,5-Cl₂ racemate 111 CH₃ 3,4-Cl₂ racemate 112CH₃ 3,5-Cl₂ racemate 113 CH₃ 3,4-Cl₂ R 114 CH₃ 3,4-Cl₂ S 115 CH₃ 2-Cl,4-F racemate 116 CH₃ 3-Cl, 4-F racemate 117 CH₃ 2-Cl, 4-Br racemate 118CH₃ 2-Cl, 4-CH₃ racemate 119 CH₃ 3-Cl, 4-CH₃ racemate 120 CH₃ 3-Cl,5-CH₃ racemate 121 CH₃ 3-Cl, 4-OCH₃ racemate 122 CH₃ 2-Br, 4-F racemate123 CH₃ 2-Br, 4-CH₃ racemate 124 CH₃ 2-CF₃, 4-F racemate 125 CH₃ 2-CF₃,4-Cl racemate 126 CH₃ 2-CF₃, 4-Br racemate 127 CH₃ 3-CF₃, 4-F racemate128 CH₃ 2,3-(CH₃)₂ racemate 129 CH₃ 2,4-(CH₃)₂ racemate 130 CH₃2,4-(CH₃)₂ R 131 CH₃ 2,4-(CH₃)₂ S 132 CH₃ 2,5-(CH₃)₂ racemate 133 CH₃2,6-(CH₃)₂ racemate 134 CH₃ 3,4-(CH₃)₂ racemate 135 CH₃ 3,4-(CH₃)₂ R 136CH₃ 3,4-(CH₃)₂ S 137 CH₃ 2-CH₃, 6-C₂H₅ racemate 138 CH₃ 2-CH₃, 3-Fracemate 139 CH₃ 2-CH₃, 4-F racemate 140 CH₃ 2-CH₃, 5-F racemate 141 CH₃2-CH₃, 3-Cl racemate 142 CH₃ 2-CH₃, 4-Cl racemate 143 CH₃ 2-CH₃, 5-Clracemate 144 CH₃ 2-CH₃, 6-Cl racemate 145 CH₃ 2-CH₃, 4-OCH₃ racemate 146CH₃ 2-CH₃, 6-OCH₃ racemate 147 CH₃ 2,6-(C₂H₅)₂ racemate 148 CH₃2,5-(CF₃)₂ racemate 149 CH₃ 3,5-(CF₃)₂ racemate 150 CH₃ 3-CF₃, 5-OCH₃racemate 151 CH₃ 3,5-(CF₃)₂ R 152 CH₃ 3,5-(CF₃)₂ S 153 CH₃ 2,4-(OCH₃)₂racemate 154 CH₃ 3,4-(OCH₃)₂ racemate 155 CH₃ 3,4-(OCH₃)₂ R 156 CH₃3,4-(OCH₃)₂ S 157 CH₃ 2-OCH₃, 4-F racemate 158 CH₃ 2-OCH₃, 5-Cl racemate159 CH₃ 2-OCH₃, 5-CF₃ racemate 160 CH₃ 2-OCH₃, 5-CH₃ racemate 161 CH₃2,3,4-F₃ racemate 162 CH₃ 2,4,5-F₃ racemate 163 CH₃ 2,3,4-Cl₃ racemate164 CH₃ 2,4,6-(CH₃)₃ racemate 165 C₂H₅ H racemate mp 55-58° C. 166 C₂H₅H R 167 C₂H₅ H S 168 C₂H₅ 2-F racemate 169 C₂H₅ 2-F R 170 C₂H₅ 2-F S 171C₂H₅ 3-F racemate 172 C₂H₅ 3-F R 173 C₂H₅ 3-F S 174 C₂H₅ 4-F racemate175 C₂H₅ 4-F R 176 C₂H₅ 4-F S 177 C₂H₅ 2-Cl racemate 178 C₂H₅ 2-Cl R 179C₂H₅ 2-Cl S 180 C₂H₅ 3-Cl racemate 181 C₂H₅ 3-Cl R 182 C₂H₅ 3-Cl S 183C₂H₅ 4-Cl racemate 184 C₂H₅ 4-Cl R 185 C₂H₅ 4-Cl S 186 C₂H₅ 2-Brracemate 187 C₂H₅ 2-Br R 188 C₂H₅ 2-Br S 189 C₂H₅ 3-Br racemate 190 C₂H₅3-Br R 191 C₂H₅ 3-Br S 192 C₂H₅ 4-Br racemate 193 C₂H₅ 2-I racemate 194C₂H₅ 3-I racemate 195 C₂H₅ 4-I racemate 196 C₂H₅ 4-Br R 197 C₂H₅ 4-Br S198 C₂H₅ 2-CH₃ racemate 199 C₂H₅ 2-CH₃ R 200 C₂H₅ 2-CH₃ S 201 C₂H₅ 3-CH₃racemate 202 C₂H₅ 3-CH₃ R 203 C₂H₅ 3-CH₃ S 204 C₂H₅ 4-CH₃ racemate 205C₂H₅ 4-CH₃ R 206 C₂H₅ 4-CH₃ S 207 C₂H₅ 3-C₂H₅ racemate 208 C₂H₅ 4-C₂H₅racemate 209 C₂H₅ 4-C₃H₇-n racemate 210 C₂H₅ 2-C₃H₇-iso racemate 211C₂H₅ 4-C₃H₇-iso racemate 212 C₂H₅ 4-C₄H₉-tert racemate 213 C₂H₅ 3-CF₃racemate 214 C₂H₅ 3-CF₃ R 215 C₂H₅ 3-CF₃ S 216 C₂H₅ 4-CF₃ racemate 217C₂H₅ 4-CF₃ R 218 C₂H₅ 4-CF₃ S 219 C₂H₅ 4-OCH₃ racemate 220 C₂H₅ 4-OCH₃ R221 C₂H₅ 4-OCH₃ S 222 C₂H₅ 2-OC₂H₅ racemate 223 C₂H₅ 3-OC₂H₅ racemate224 C₂H₅ 4-OC₂H₅ racemate 225 C₂H₅ 4-OC₃H₇-iso racemate 226 C₂H₅ 3-OCF₃racemate 227 C₂H₅ 4-OCF₃ racemate 228 C₂H₅ 4-OCHF₂ racemate 229 C₂H₅4-OCH₂CF₃ racemate 230 C₂H₅ 2-SCH₃ racemate 231 C₂H₅ 3-SCH₃ racemate 232C₂H₅ 4-SCH₃ racemate 233 C₂H₅ 4-SC₂H₅ racemate 234 C₂H₅ 4-SC₃H₇-isoracemate 235 C₂H₅ 4-S(O)CH₃ racemate 236 C₂H₅ 4-SO₂CH₃ racemate 237 C₂H₅3-SCF₃ racemate 238 C₂H₅ 4-SCH₂CF₃ racemate 239 C₂H₅

racemate 240 C₂H₅

racemate 241 C₂H₅

racemate 242 C₂H₅ 2-CO₂CH₃ racemate 243 C₂H₅ 2-CO₂C₂H₅ racemate 244 C₂H₅4-NO₂ racemate 245 C₂H₅ 4-CN racemate 246 C₂H₅ 2,3-F₂ racemate 247 C₂H₅2,4-F₂ racemate 248 C₂H₅ 2,4-F₂ R 249 C₂H₅ 2,4-F₂ S 250 C₂H₅ 2,5-F₂racemate 251 C₂H₅ 2,6-F₂ racemate 252 C₂H₅ 3,4-F₂ racemate 253 C₂H₅3,4-F₂ R 254 C₂H₅ 3,4-F₂ S 255 C₂H₅ 3,5-F₂ racemate 256 C₂H₅ 2-F, 4-Clracemate 257 C₂H₅ 2-F, 4-Br racemate 258 C₂H₅ 2-F, 5-CF₃ racemate 259C₂H₅ 2-F, 4-OCH₃ racemate 260 C₂H₅ 3-F, 6-CF₃ racemate 261 C₂H₅ 3-F,3-CF₃ racemate 262 C₂H₅ 3-F, 4-CH₃ racemate 263 C₂H₅ 3-F, 5-CH₃ racemate264 C₂H₅ 2,3-Cl₂ racemate 265 C₂H₅ 2,4-Cl₂ racemate 266 C₂H₅ 2,4-Cl₂ R267 C₂H₅ 2,4-Cl₂ S 268 C₂H₅ 2,6-Cl₂ racemate 269 C₂H₅ 2,5-Cl₂ racemate270 C₂H₅ 3,4-Cl₂ racemate 271 C₂H₅ 3,5-Cl₂ racemate 272 C₂H₅ 3,4-Cl₂ R273 C₂H₅ 3,4-Cl₂ S 274 C₂H₅ 2-Cl, 4-F racemate 275 C₂H₅ 3-Cl, 4-Fracemate 276 C₂H₅ 2-Cl, 4-Br racemate 277 C₂H₅ 2-Cl, 4-CH₃ racemate 278C₂H₅ 3-Cl, 4-CH₃ racemate 279 C₂H₅ 3-Cl, 5-CH₃ racemate 280 C₂H₅ 3-Cl,4-CH₃O racemate 281 C₂H₅ 2-Br, 4-F racemate 282 C₂H₅ 2-Br, 4-CH₃racemate 283 C₂H₅ 2-CF₃, 4-F racemate 284 C₂H₅ 2-CF₃, 4-Cl racemate 285C₂H₅ 2-CF₃, 4-Br racemate 286 C₂H₅ 3-CF₃, 4-F racemate 287 C₂H₅2,3-(CH₃)₂ racemate 288 C₂H₅ 2,4-(CH₃)₂ racemate 289 C₂H₅ 2,4-(CH₃)₂ R290 C₂H₅ 2,4-(CH₃)₂ S 291 C₂H₅ 2,5-(CH₃)₂ racemate 292 C₂H₅ 2,6-(CH₃)₂racemate 293 C₂H₅ 3,4-(CH₃)₂ racemate 294 C₂H₅ 3,4-(CH₃)₂ R 295 C₂H₅3,4-(CH₃)₂ S 296 C₂H₅ 2-CH₃, 6-C₂H₅ racemate 297 C₂H₅ 2-CH₃, 3-Fracemate 298 C₂H₅ 2-CH₃, 4-F racemate 299 C₂H₅ 2-CH₃, 5-F racemate 300C₂H₅ 2-CH₃, 3-Cl racemate 301 C₂H₅ 2-CH₃, 4-Cl racemate 302 C₂H₅ 2-CH₃,5-Cl racemate 303 C₂H₅ 2-CH₃, 6-Cl racemate 304 C₂H₅ 2-CH₃, 4-OCH₃racemate 305 C₂H₅ 2-CH₃, 6-OCH₃ racemate 306 C₂H₅ 2,6-(C₂H₅)₂ racemate307 C₂H₅ 2,5-(CF₃)₂ racemate 308 C₂H₅ 3,5-(CF₃)₂ racemate 309 C₂H₅3-CF₃, 5-OCH₃ racemate 310 C₂H₅ 3,5-(CF₃)₂ R 311 C₂H₅ 3,5-(CF₃)₂ S 312C₂H₅ 2,4-(OCH₃)₂ racemate 313 C₂H₅ 3,4-(OCH₃)₂ racemate 314 C₂H₅3,4-(OCH₃)₂ R 315 C₂H₅ 3,4-(OCH₃)₂ S 316 C₂H₅ 2-OCH₃, 4-F racemate 317C₂H₅ 2-OCH₃, 5-Cl racemate 318 C₂H₅ 2-OCH₃, 5-CF₃ racemate 319 C₂H₅2-OCH₃, 5-CH₃ racemate 320 C₂H₅ 2,3,4-F₃ racemate 321 C₂H₅ 2,4,5-F₃racemate 322 C₂H₅ 2,3,4-Cl₃ racemate 323 C₂H₅ 2,4,6-(CH₃)₃ racemate

SYNTHESIS EXAMPLE 2 (Intermediate)

(S)-α-methylbenzyl isocyanate (8.00 g), trimethylsilyl azide (9.40 g)and a catalytic amount of boron trifluoride-ether-complex were mixed andrefluxed for 16 hours on heating. The excess amount of trimethylsilylazide was distilled off under reduced pressure and the residue wastreated by silica gel column chromatography (eluant: hexane: ethylacetate=3:2) to obtain 1-((S)-α-methylbenzyl)-5(4H)-tetrazolinone (8.18g). mp: 102-106° C.

SYNTHESIS EXAMPLE 3 (Intermediate)

Sodium azide (1.95 g) was suspended in anhydrous dimethylformamide (18ml) and anhydrous aluminium chloride (0.2 g) was added in an argonstream under ice cooling and stirred for 15 minutes. Then(S)-α-methylbenzyl isocyanate (4.85 g) was added drop by drop and thereaction mixture was stirred for 3 hours in argon stream on heating at70-75° C. After natural cooling, the reaction mixture was added to amixture of sodium sulfite (0.5 g), water (100 ml) and ice (50 g) onstirring, acidified with 10% hydrochloric acid and extracted with ethylacetate. After drying the organic layer with anhydrous sodium sulfate,the solvent was distilled off under reduced pressure and the residue wastreated by silica gel column chromatography (eluant: hexane: ethylacetate=3:2) to obtain 1-((S)-α-methylbenzyl)-5(4H)-tetrazolinone (3.20g). mp: 102-106° C.

The compounds obtained according in a similar way as the above-mentionedSynthesis Examples 2 or 3 are listed in the following Table 2 togetherwith the compounds obtained in the Synthesis Examples 2 and 3.

TABLE 2

Compound No. R¹ *R/S Property II-1 CH₃ racemate II-2 CH₃ R mp 97-106° C.II-3 CH₃ S mp 102-106° C. II-4 C₂H₅ racemate mp 103-106° C. II-5 C₂H₅ RII-6 C₂H₅ S

TEST EXAMPLE 1 Test for Herbicidal Effect Against Paddy Field Weeds

Preparation of formulation of the active compound

Carrier: Acetone 5 parts by weight

Emulsifier: Benzyloxypolyglycolether 1 part by weight

A formulation of the active compound is obtained as an emulsion bymixing 1 part by weight of the active compound with the above-mentionedamount of carrier and emulsifier. A prescribed amount of saidformulation is diluted with water to prepare a formulation for testing.

Test method

In a greenhouse 3 seedlings of paddy rice (cultivar: Nipponbare) of 2.5leafstage (15 cm tall) were transplanted in a 500 cm² pot filled withpaddy field soil. Then seeds of barnyard grass, smallflower, bulrush,monochoria and broad-leaved weeds (common false pimpernel, Indiantoothcup, long stemmed water wort, Ammannia multiflora Roxb., Dopatriumjunceum Hammilt etc.) were sown and water was poured on the soil to adepth of about 2-3 cm.

5 days after the rice transplantation a formulation of each activecompound prepared according to the aforementioned preparation method wasapplied to the surface of the water. A water depth of 3 cm wasmaintained. The herbicidal effect was examined after 3 weeks from thetreatment. The herbicidal effect was rated as 100% in the case ofcomplete death and as 0% in the case of no herbicidal effect.

As a result, the compounds No. 2, 3, 11, 12, 42, 88 and 165 of thepresent invention showed at an application rate of 0.5 kg/ha sufficientherbicidal effect against paddy field weeds and showed safety to thetransplanted paddy rice.

FORMULATION EXAMPLE 1 Granule

To a mixture of 5 parts by weight of compound No. 165, 30 parts byweight of bentonite (montmorillonite), 58 parts by weight of talc and 2parts by weight of ligninsulphonate, 25 parts by weight of water wereadded. The mixture is well kneaded, made into granules of 10-40 mesh byextrusion granulation and dried at 40-50° C. to obtain granules.

FORMULATION EXAMPLE 2 Granule

95 parts by weight of clay mineral particles having a particle sizedistribution of 0.2-2 mm are put in a rotary mixer. While rotating it, 5parts by weight of the compound No. 2 are sprayed together with a liquiddiluent into the mixer, wetted uniformly and dried at 40-50° C. toobtain granules.

FORMULATION EXAMPLE 3 Emulsifiable Concentrate

30 parts by weight of the compound No. 3, 5 parts by weight of xylene, 8parts by weight of polyoxyethylenealkyl phenyl ether and 7 parts byweight of calcium alkylbenzenesulphonate are mixed and stirred to obtainan emulsion.

FORMULATION EXAMPLE 4 Wettable Powder

15 parts by weight of the compound No. 42, 80 parts by weight of amixture of white carbon (hydrous amorphous silicon oxide fine particles)and powder clay (1:5), 2 parts by weight of sodiumalkylbenzenesulphonate and 3 parts by weight of sodiumalkylnaphthalenesulphonate-formalin-polymer are mixed in powder form andmade into a wettable powder.

FORMULATION EXAMPLE 5 Water Dispersible Granule

20 parts by weight of the compound No. 2, 30 parts by weight of sodiumligninsulphonate, 15 parts by weight of bentonite and 35 parts by weightof calcined diatomaceous earth powder are well mixed, added with water,then extruded using a 0.3 mm screen and dried to obtain a waterdispersible granule.

What is claimed is:
 1. A compound according to the Formula (I)

wherein R¹ represents methyl or ethyl, R² represents halogen, alkyl,haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl,alkylsulfonyl, phenyl, phenoxy, alkoxycarbonyl, nitro or cyano, and nrepresents 0, 1, 2, 3, 4 or
 5. 2. The compound according to claim 1wherein R¹ represents methyl or ethyl, R² represents fluoro, chloro,bromo, C₁₋₄ alkyl, C₁₋₄ haloalkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkoxy, C₁₋₄alkylthio, C₁₋₄ haloalkylthio, C₁₋₄ alkylsulfinyl, C₁₋₄ alkylsulfonyl,phenyl, phenoxy, C₁₋₄ alkoxycarbonyl, nitro or cyano, and n represents0, 1, 2, 3 or
 4. 3. The compound according to claim 1 wherein R¹represents methyl, R² represents fluoro, chloro, methyl, ethyl,n-propyl, isopropyl, tertbutyl, trifluoromethyl, methoxy, ethoxy,isopropoxy, trifluoromethoxy, difluoromethoxy, 2,2,2-trifluoroethoxy,methylthio, ethylthio, isopropylthio, methylsulfinyl, methylsulfonyl,phenyl, phenoxy, methoxycarbonyl, ethoxycarbonyl, nitro or cyano, and nrepresents 0,1,2, or
 3. 4. A process for the preparation of a compoundof the Formula (I)

wherein R¹ represents methyl or ethyl, R² represents halogen, alkyl,haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl,alkylsulfonyl, phenyl, phenoxy, alkoxycarbonyl, nitro or cyano, and nrepresents 0, 1, 2, 3, 4 or 5,  comprising the step of: a) reacting acompound of the Formula (II)

 wherein R¹ is as defined above, with a compound of the Formula (III)

 wherein R² and n are as defined above, and M represents a leaving groupin the presence of an inert solvent and, optionally, in the presence ofa base.
 5. An herbicidal composition comprising a compound of theFormula (I) according to claim 1 and a herbicidally acceptable carrier.6. A process for controlling weeds comprising the step of allowing aneffective amount of a compound of the Formula (I) according to claim 1to act on a member selected from the group consisting of weeds, ahabitat of said weeds, and combinations thereof.
 7. A process forcontrolling weeds comprising the step of allowing an effective amount ofa herbicidal composition to act on a member selected from the groupconsisting of weeds, a habitat of said weeds and combinations thereof,wherein said herbicidal composition comprises a compound of the Formula(I) according to claim 1 and a member selected from the group consistingof an extender, a surfactant and combinations thereof.
 8. A process forthe preparation of a herbicidal composition comprising the step ofmixing a compound of the Formula (I) according to claim 1 with a memberselected from the group consisting of an extender, a surface activeagent and combinations thereof.
 9. The process of claim 4, wherein saidleaving group of radical M is selected from the group consisting ofchloro and bromo.